Polymers with varied and useful properties may be produced in processes using at least two polymerization catalysts, at least one of which is a selected nickel polymerization catalyst, for the synthesis of polyolefins.
Polyolefins are most often prepared by polymerization processes in which a transition metal containing catalyst system is used. Depending on the process conditions used and the catalyst system chosen, polymers, even those made from the same monomer(s) may have varying properties. Some of the properties which may change are molecular weight and molecular weight distribution, crystallinity, melting point, and glass transition temperature. Except for molecular weight and molecular weight distribution, branching can affect all the other properties mentioned.
It is known that certain transition metal containing polymerization catalysts, especially those containing late transition metals such as nickel, are especially useful in varying the branching in polyolefins made with them, see for instance World Patent Applications 96/23010 and 97/02298, and U.S. patent application Ser. No. 09/006,628, filed Jan. 13, 1998 (now U.S. Pat. No. 6,060,569), and Ser. No. 09/006,536, filed Jan. 13, 1998 (now U.S. Pat. No. 6,174,975), and World Patent Applications 98/30610 and 98/30609. It is also known that blends of distinct polymers, that vary for instance in the properties listed above, may have advantageous properties compared to xe2x80x9csinglexe2x80x9d polymers. For instance it is known that polymers with broad or bimodal molecular weight distributions may be melt processed (be shaped) more easily than narrower molecular weight distribution polymers. Similarly, thermoplastics such as crystalline polymers may often be toughened by blending with elastomeric polymers.
Therefore, methods of producing polymers which inherently produce polymer blends are useful especially if a later separate (and expensive) polymer mixing step can be avoided. However in such polymerizations one should be aware that two different catalysts may interfere with one another, or interact in such a way as to give a single polymer.
This invention concerns a process for the polymerization of olefins, comprising, contacting under polymerizing conditions:
(a) a first active polymerization catalyst for said olefins which contains a Ni complex of a ligand selected from the group consisting of: 
or a compound of the formula 
wherein:
Ar1, Ar2, Ar4, Ar5, Ar10, Ar11, Ar12 and Ar13 are each independently aryl or substituted aryl;
R1 and R2 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R1 and R2 taken together form a ring, and R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R1, R2 and R3 taken together form a ring;
A is a xcfx80-allyl or xcfx80-benzyl group;
R10 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R11, R12, R13, R14, R16, R17, R18, R19, R20, R21, R30, R31, R32, R33, R34, R35, R50, R51, R52, R53 and R54 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR27;
R22 is hydrocarbyl, substituted hydrocarbyl, xe2x80x94SR117, xe2x80x94OR117, or xe2x80x94NR1182, R24 is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R27 is hydrocarbyl or substituted hydrocarbyl, and provided that R22 and R24 or R24 and R27 taken together may form a ring;
R60, R61, R62 and R63 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R64 and R65 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar14, Ar15, Ar16, Ar17, Ar18 and Ar19 are each independently hydrocarbyl or substituted hydrocarbyl;
R117 is hydrocarbyl or substituted hydrocarbyl;
each R118 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR57 and L is CR55;
R55, R56 and R57 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R55, R56 and R57 taken together form a ring;
R67 is hydrogen, alkyl or substituted alkyl;
R77 is hydrocarbyl or substituted hydrocarbyl;
Ar3 is hydrocarbyl or substituted hydrocarbyl;
R79,R80, R81, R82, R83,R84, R85, R86, R87, R88 and R89 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R90, R91, R92 and R93 are each independently hydrocarbyl or substituted hydrocarbyl;
R94 and R95 are each independently hydrocarbyl or substituted hydrocarbyl;
R96, R97, R98, and R99 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR108 wherein R108 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R100, R101, R102, R103, R104, R105, R106, and R107 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R109, R110, R111, R112, R113, R114, R115 and R116 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
s is an integer of 1 or more; and
R28 and R29 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
(b) a second active polymerization catalyst for said olefins which contains one or more transition metals;
(c) a least one first olefin capable of being polymerized by said first active polymerization catalyst; and
(d) at least one second olefin capable of being polymerized by said second active polymerization catalyst.
This invention also concerns a polymerization catalyst component, comprising:
(a) a first active polymerization catalyst for said olefins which contains a Ni complex of a ligand selected from the group consisting of: 
or a compound of the formula 
wherein:
Ar1, Ar2, Ar4, Ar5, Ar10, Ar11, Ar12 and Ar13 are each independently aryl or substituted aryl;
R1 and R2 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R1 and R2 taken together form a ring, and R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R1, R2 and R3 taken together form a ring;
A is a xcfx80-allyl or xcfx80-benzyl group;
R10 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R11, R12, R13, R14, R16, R17, R18, R19, R20, R21, R30, R31, R32, R33, R34, R35, R50, R51, R52, R53 and R54 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR27;
R22 is hydrocarbyl, substituted hydrocarbyl, xe2x80x94SR117, xe2x80x94OR117, or xe2x80x94NR1182, R24 is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R27 is hydrocarbyl or substituted hydrocarbyl, and provided that R22 and R24 or R24 and R27 taken together may form a ring;
R60, R61, R62 and R63 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R64 and R65 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar14, Ar15, Ar16, Ar17, Ar18 and Ar19 are each independently hydrocarbyl or substituted hydrocarbyl;
R117 is hydrocarbyl or substituted hydrocarbyl;
each R118 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR57 and L is CR55;
R55, R56 and R57 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R55, R56 and R57 taken together form a ring;
R67 is hydrogen, alkyl or substituted alkyl;
R77 is hydrocarbyl or substituted hydrocarbyl;
Ar3 is hydrocarbyl or substituted hydrocarbyl;
R79, R80, R81, R82, R83, R84, R85, R86, R87, R88 and R89 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R90, R91, R92 and R93 are each independently hydrocarbyl or substituted hydrocarbyl;
R94 and R95 are each independently hydrocarbyl or substituted hydrocarbyl;
R96, R97, R98, and R99 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR108 wherein R108 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R100, R101, R102, R103, R104, R105, R106, and R107 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R109, R110, R111, R112, R113, R114, R115 and R116 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
s is an integer of 1 or more; and
R28 and R29 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
(b) a second active polymerization catalyst for said olefins which contains one or more transition metals;
(c) a catalyst support; and
(d) optionally one or more polymerization catalyst activators for one or both of (a) and (b).